Manufacture of polychrome pictures



Nov. 7, 1939.

Filed April 4, 1956 tented Nov. 7, 1939 UNITED STATES t 2,ll9,238 PATENT FFICE MANUFACTURE 0F POLYCHROME PICTURES `Application April 4, 1936, Serial No. 72,718 In Germany April 10, 1935 10 Claims.

Our present invention relates to the manufacture of polychrome pictures and more particularly to the manufacture of polychrome pictures from photographic silver halide emulsions.

One of its objects is to provide a process for the production of improved polychrome pictures from silver halide emulsions. Another object are the improved photographic silver halide emulsion layers containing a component which produces color in the developer. Further objects will be seen from the detailed specification following hereafter.

It is known that layers of silver halide emulsion can be developed in color by permitting the products of reaction, produced during the development from developer constituents which have a free amino-group, to condense with reactive phenols or amines to form quinone-imine dyestuifs` as for instance indoamines, lndoanllines, and indophenols. Dyestu formation also occurs with bodies which contain a reactive methylene group in which case azomethines are produced. Since, however, in the methods hitherto applied for development in color the component which produces color is incorporated in the developer the Vmethod leads merely to monochrome pictures. Attempts to incorporate in the emulsion layer the substance that produces the color have failed, particularly when several layers are used one above the other for producing a polychrome picture. In this case either in` applying the second or a later layer to the first layer, or in bringing the material arranged in one or more layers into the developing solution, the components in the emulsion that produce color and are generally soluble in alkali, pass into the adjacent layer into the developer.

The present invention relates to a process in which such diiusion is prevented and the components are fixed in the several colloidal layers. For this purpose there is introduced into the dyestuff component a group which lends the component substantive character with respect to the binding agent of the silver halide emulsion, that is to say, which prevents diffusion in the binding agent of the silver halide emulsion. By introduction of such a group the component can be dissolved in a water-soluble or alkalisoluble form in the colloid without fear that in the finished photographic material the component will diiuse into the adjacent layer or layers. The substantive character produced by introduction of the group can be further strengthened by means of an agent which has a precipitating action on or by means of a group which increases the molecular dimensions of the component. Agents which have a precipitating action are, for instance, diphenylguanidide and diphenylbiguanidide. Groups which increase the molecular dimensions of the component are, for

(Cl. SI5-6) instance, amino groups, benzoyl groups and benzoyl amino groups which are introduced between t-he component which produces color and the component which imparts substantive character.

Suitable groups for imparting such substantive character and therefore suitable for introduction into the hitherto known color-producers are, for example, diphenyl, dianlsidine, tolidine, diphenylcarboxylic acid, diamino-benzoylamino-diphenyl, stilbene, di-aminostilbene, diamino-benzoylaminostilbene, azoxybenzene, hydroxynaphthoic acid-amides, such as 2,3-hydroxynaphthoic acid and 4-(2,3)-hydroxynaphthoylamino-aniline, diaryl-ureas such as diamine-diphenylurea, diamino-benzoylamino-dlphenylurea, and

the urea from amino-benzoylamino-o-sulfanilic acid, benzthiazole, dehydrothiotolidine, aminonaphthols, such as 2-amino-5-naphthole-7sul ionic acid and 2-aminobenzoylamino--naphthole-'I-sulfonic acid, terephtaloylbisacetlc ester, 2,3-hydroXyanthracene-carboxylic acid, 2,3-hydroxycarbazole-carboxylic acid, aminochrysene, aminopyrene, and aminonaphthylene-oxide, or the like. Components for producing color into which these groups are to be introduced are,v for example, phenols such as m-aminophenol, o-o'- dinaphthole, o-hydroxydiphenyl, thymol, 2,5-d (phenylamino)phenol, aniline, naphthols, such as a-naphthol, a-hydroxynaphthoic acid, chloronaphthole and trichloronaphthole, naphthylamine, for instance, a-naphthylamine, aminonaphthols, for instance, 1,5-aminonaphthole, and all compounds which contain a reactive methylene group, for instance aceto-acetic esters, for instance, bromo-acetoacetic acid ester and acetoacetic anilide, cyano-acetic esters, for instance, cyanacetic acid ester, benzoyl-acetic esters, for instance, benzoylacetic anidide, hydrindenes. for instance, diketohydrinden, pyrazolones, such as phenylmethylpyrazolone and 1-phenyl-3 phenylpyrazolone, coumaranones, malonic acid anilide, w-cyanaceto-phenon, hydroxythionaphthene, and the like.

The following example illustrates the invention:

'I'he three-color layers, which may be arranged on one or both sides of the support, contain as components for producing color:

methyl--pyrazolone for red development, 2. Terephthaloylbiacetic acid-anilide for yellow, 3, 3,5-di(phenylamino)phenol for blue-green.

The alkali salts of these bodies, dissolved in methanol, are stirred into a gelatin solution of 10 per cent strength in the proportion of 1 gram to 50 cc. of the gelatin solution, and the solution is then mixed with cc. of silver halide emulsion. A suitable developer is one consisting of 1 gram of diethylamino-anilide-hydrochloride, 6 grams of potassium carbonate and 100 cc. of water, to which sulilte may be added, if desired.

As it is shown in the example aforesaid, the substantive groups may be introduced into the color components by means of an amide linkage. Thus, for instance, hydroxynaphthoic acid chloride may be condensed with 1-paminophenyl 3-methyl-5-pyrazolone so that an amide is formed by the carboxyl group of the hydroxynaphthoic acid and the amino group of the pyrazolone. The substantive groups may be introduced also by means of an ester linkage. It is again possible to directly connect the compounds.

The single flgure of the accompanying drawing shows a film in accordance with the in- 'Vention having a support I coated with a silver halide emulsion layer 2 containing a color component having a group which imparts substantivity to the binding agent.

What we claim is:

1. A light-sensitive material for color photography comprising a silver halide emulsion containing a dyestui component for color forming development having attached thereto a group which lends said component substantive char- 'acter with respect to the binding agent of the silver halide emulsion and further containing a compound having a precipitating action on said dvestui component.

2. In a process of producing photographic `*color pictures the step which comprises treating an exposed photographic material having a silver halide emulsion containing a component for dyestuff forming development having attached thereto a group which lends said component substantive character with respect to the binding agent of the silver halide with a solution of a developing substance having an unsubstituted amino-group in order to produce the color.

3. In a process of producing photographic colored pictures, the step which comprises developing by means of an amino-developer an exposed photographic material having a silver halide emulsion containing a dyestui component for color forming development having attached thereto a group which renders said component fast to diiusion in the binding agent of the silver halide emulsion,.said group comprising at least two organic rings.

4. In a process of producing photographic co1- ored pictures, the step which comprises developing by means of an amino-developer an exposed photographic material having a silver halide emulsion containing a dyestui component for color forming development having attached thereto a group which renders said component fast to diffusion in the binding agent of the silver halide emulsion, said group comprising at least ten carbon atoms.

5. A light-sensitive material for color photography comprising a silver halide emulsion containing a mononuclear phenolic dyestuff component for color forming development having attached thereto a group which lends said component substantive character with respect to the binding agent of the silver halide emulsion, said group comprising at least two -membered aromatic rings.

6. The process as dened in claim 3. wherein at least 2 of said ringsare selected from the class consisting of fused rings and rings joined together by a linkage selected from the class consisting of a nuclear carbon to nuclear carbon linkage, an acid amide linkage, a -CH=CH- linkage, a -NON- linkage, and a -NHCONH- linkage.

7. 'I'he process as' defined in claim 3, wherein at least 1 of said rings is a heterocyclic ring.

8. A light-sensitive material for color photography comprising a silver halide emulsion containing a dyestu component for color forming development, .selected from the class consisting of mononuclear phenolic dyestuff components and acyl acetic ester dyestui components, having attached thereto a group which renders said component fast to diffusion in the binding agent of the silver halide emulsion, said group comprising at least two G-membered aromatic rings.

9. A light-sensitive material as defined in claim 8, wherein the component for color forming is an aceto acetic ester.

l0. A light-sensitive material as dened in claim 8, wherein the component for color development is a cyanaoetic ester.

GUSTAV WIIMANNS. WILHELM SCHNEIDER. ERNST BAUER. 

